Institute of Chemistry, Carl von Ossietzky University of Oldenburg , Carl von Ossietzky-Str. 9-11, 26129 Oldenburg, Federal Republic of Germany.
J Am Chem Soc. 2016 May 11;138(18):6061-7. doi: 10.1021/jacs.6b02824. Epub 2016 Apr 27.
The synthesis of hydridosilylenes Ter(H)Si: 3a (Ter: 2,6-bis(2,4,6-trimethylphenyl)phenyl) and Ter*(H)Si: 3b (Ter*: 2,6-bis(2,4,6-triiso-propylphenyl)phenyl) stabilized by the N-heterocyclic carbene (NHC) ImMe4 is reported. The synthesis of stabilized hydridosilylenes 3 was accomplished by a previously unknown NHC-induced fragmentation of silanorbornadiene derivatives. Structural studies of the stabilized silylenes 3 and of its Fe(CO)4 complex 12 accompanied by a theoretical analysis of their bonding situation indicate that stabilized silylenes such as 3 can be regarded as neutral silyl anion equivalents. A computational investigation of the reaction course indicate a virtual one-step reaction between the NHC and the silanorbornadiene. A theoretical assessment of the scope and limitations of this reaction suggests that it is general and can be used also for the synthesis of other carbene analogues such as germylenes and phosphinidenes.
报道了由 N-杂环卡宾（NHC）ImMe4 稳定的氢硅烯 Ter(H)Si: 3a（Ter：2,6-双（2,4,6-三甲基苯基）苯基）和 Ter*(H)Si: 3b（Ter*：2,6-双（2,4,6-三异丙基苯基）苯基）的合成。通过先前未知的 NHC 诱导的硅烷降冰片二烯衍生物的碎裂，完成了稳定氢硅烯 3 的合成。稳定的硅烯 3 及其 Fe(CO)4 配合物 12 的结构研究以及对其成键情况的理论分析表明，像 3 这样的稳定硅烯可以被视为中性硅基阴离子等价物。对反应过程的计算研究表明，NHC 与硅烷降冰片二烯之间发生了虚拟的一步反应。对该反应的范围和限制的理论评估表明，该反应是通用的，也可用于合成其他卡宾类似物，如锗烯和膦烯。
